Process for the production of aliphatic or cycloaliphatic primary amines



' aluminum-, magnesium-,

ample.

Patented Mar. 10, was

UNITED STATES PATENT OFFICE 2.033.866 rnocass ron THE raonuc'non or m- PHATIC AMINES OR CYCLOALIPHATIO PRIMARY' No Drawing. Application August 12,1932, Serial The method discovered by Sabatier and Mailhe for converting the aliphatic alcoholswlth ammonia into aminesin the presence of catalytic substances at elevated temperatures requires temperatures above 300 C. and produces yields containing only relatively small quantities of primary amines, because even by the use of excess ammonia always secondary amines and unsaturated hydrocarbons, the condensation products thereof and ethers are produced as undesirable by-products.

Now it has been found that it is possible to use this reaction for production of primary amines from higher molecular aliphatic alcohols or naphthenic alcohols in a more profitable manner if the conversion is carried out at higher pressures., By this process the amines are produced in a technical measure the above mentioned disadvantages are considerably avoided because the formation of by-products amounts to less than 10%. Moreover the activity of the catalysts used is preserved for a very long time in spite of much use with a greater conversion of the products treated. Higher molecular aliphatic alcohols containing 8 carbon atoms or more are found as especially adapted for this conversion. It has been found in ac-- cordance with the present invention that even at relatively low pressures a more favourable conversion is obtained than when proceeding according to the method specified by Sabatier. It is advantageous however to carry out the reaction at higher pressures especiallyvat-" pressures above fating catalystsv atmospheres. The de known in the literature are ble. as .ior instance metallic oxides, whereof hum-oxide are especially adapted. These metal oxides are suitable for use alone or in admixture with each other in the form oi mixed catalysts. This reaction proceeds at temperatures between 300 and 450 C. and in the presence of an excess of ammonia. the unconsumed parts or which can be conducted anew to the reaction space after separating the products formed.

The amines produced according to the process in question are useful for combating insect pests, as wetting-out agents and for treating rubber. In the following the process will be illustratedby a few typical examples, without'confining it to the special modes in action described in any ex- Ezample I It 1 part by volume of cetyl alcohol which is Y 01' 94 to 95% cetyl amine.

in a very good yield and" amongothers thorium-, molybde- In Germany August 13, 1931 10 Claims. (Cl. 260-127) -tery-oily liquid is obtained from the resulting vapours when condensed. This liquid finally coagulates partially and by distillation gives a yield Example 11 If instead of cetyl alcohol as described in Example I, the higher molecular' fatty alcohols obtained by the reduction of cocoanut-oil or palmkernel oil, which boil at 10 mm. pressure of mercury between 85 and C. are treated in the same manner a yield of 93 to 95% of a mixture of primary amines is obtained containing especially dodecyl amine.

Example Ill From naphthenic alcohols (acetyl saponiflcation number 206), which at 20 mm. pressure of mercury distill over between 90 and 206 C. and which are obtained by reduction of commercial naphthenic acid, a yield of about 90-92% of the corresponding primary amines is obtained at 350- 380 C. and under a pressure of 180 atmospheres by passing the alcohols with 3 to 4 times their volume of ammonia over a contact catalyst consisting of equal part of thorium-oxide and aluminum-oxide consolidated by chromic acid.

ffxample IV at temperatures of about 300 to about 450 C.

in the presence of dehydrating metal oxide.

2. The method of producing primary amines which comprises reacting aliphatic alcohols having 8 or more carbon atoms in the molecule with ammonia at super-atmospheric pressure-in the presence 01' dehydrating metal oxide.

'3. The method of producing primary which comprises reacting aliphatic alcohols having 8 or more carbon atoms in the molecule with ammonia at super-atmospheric pressure and at temperatures of about 300 to about 450 C. in the presence of dehydrating metal oxide.

e. The method of producing primary amines which comprises reacting aliphatic alcohols having 8 or more carbon atoms in the molecule with ammonia at pressures above 50 atmospheres in the presence of dehydrating metal oxide.

5. The method of producing primary amines which comprises reacting aliphatic alcohols having 8 or more carbon atoms in the molecule with ammonia at pressures above 50 atmospheres and at temperatures of about 300 to about 450 C. in the presence of dehydrating metal oxide.'

6. The method of producing primary amines which comprises reacting cetyl alcohol with ammonia at a pressure of about 120 to about 130 atmospheres at a temperature of about 380 to about 400 C. in the presence or dehydrating metal oxide.

the reduction of cocoanut a pressure of about 120 to about 130 atmospheres and at a temperature of about 380 to about 400 C. in the presence of dehydrating metal oxide.

8. The method of producing primary amines which comprises reacting naphthenic alcohol,

ing 8 or more carbon atoms in the molecule with ammonia at pressures above 50 atmospheres and at temperatures of about 300 to about 450 C. in the presence of a catalyst of the group consisting of aluminum oxide, magnesium oxide and thorium oxide.

WALTHER SCI-IRAUTH. 

